A pumped heat energy storage (PHES) system based on a Rankine cycle for supercritical working fluids, such as carbon dioxide and ammonia, accounting for the irreversible latent and sensible heat transfers between the working fluid and the storage liquid medium, as water or thermal oil, is analyzed. The model also includes several parameters such as pressure losses, heat exchanger efficiencies, and isentropic efficiencies of the compressor, pump, and expansion devices (such as turbines and valves), that take into account the main internal and external losses and heat leak to the environment. The model allows for the calculation of specific energy, the heat pump performance coefficient, heat engine efficiency, and overall round-trip efficiency, as well as the temperatures of the working fluid and reservoirs. A zero-dimensional model is also used to determine the time dependence of heat leak in the tanks. The main results show that this technology could achieve round trip efficiency values in the order of 50–70%. Irreversibilities in compression and expansion appears as the most influential energy losses factor. The time effect of the ambient conditions on the tanks has been analyzed for a wet subtropical climate but it seems that the ambient conditions have no major influence on the performance of the system. In addition, explicit numerical results and temperature–entropy plots are presented for two representative systems as carbon dioxide-water and ammonia-thermal oil to take into account the main values in an operating condition.